Coprecipitation method for making multi-component catalysts



United States Patent 3,401,125 COPRECIPITATION METHOD FOR MAKINGMULTI-COMPONENT CATALYSTS Joseph Jaffe, Berkeley, Calif., assignor toChevron Research Company, San Francisco, Calif., a corporation ofDelaware No Drawing. Continuation-impart of application Ser. N 0.369,583, May 22, 1964. This application July 29, 1966, Ser. No. 568,760The portion of the term of the patent subsequent to Oct. 18, 1983, hasbeen disclaimed 4 Claims. (Cl. 252-439) ABSTRACT OF THE DISCLOSUREMethod for producing a coprecipitated solid, comprising coprecipitatinga mixture of at least three different metal compounds at a pH of about5.5 to 8, said compounds including a met-a1 compound havinghydrogenating activity, a metal chloride, and a titanium compound.

This application is a continuation-in-part of copending application Ser.No. 369,583, filed May 22, 1964, now US. Patent 3,280,040.

INTRODUCTION This invention relates to a method for producing solid,coprecipitated mixtures containing at least one metal oxide and alsohaving a minimum of three components, all of said components having beencoprecipitated simultaneously.

As is well known to those skilled in the catalyst art, a gel, includingboth xerogels and aerogels, is produced by dehydration, generally byheating, of a hydrogel or gelatinous precipitate. A hydrogel can bedefined as a rigid material containing a continuous phase of a networkof colloidal particles and an imbibed liquid phase. A gelatinousprecipitate is similar to a hydrogel but without the characteristic of arigid structure. It is also well known that metal oxide-containing gelshave long been employed as catalysts and/or catalyst supports. Numerousmethods of making such composites have been suggested, most of whichhave been directed to the particular components of the initial gel, themanner of forming the gel, and in various techniques for removingundesirable components from the formed gel.

OBJECTS An object of the present invention is to provide a process forproducing catalysts, particularly hydrocr-acking and denitrificationcatalysts, that have unusually high activity for thier intendedpurposes. Another object is to provide a process for manufacturingcertain catalysts of greater regenerability than other similarcatalysts. Further objects will be apparent from the disclosures herein.

STATEMENT OF INVENTION The present invention is directed to a method forproducing a coprecipitated solid containing at least one metal oxide andhaving a minimum of three components therein, said components havingbeen coprecipit'ated simultaneously, which comprises the steps:

(a) Coprecipitating a mixture of at least three different metalcompounds at a pH of from about 5.5 to about 8, said mixture having allof the following characteristics,

(1) said mixture being a solution or a sol,

(2) at least one of said metal compounds being a compound of a metalwhose solid oxide has catalytic isomerization activity, alone or inadmixture with a diiferent metal compound,

(3) at least one of said metal compounds being a compound of a metal,the sulfide, oxide or metal form of which has catalytic hydrogenationactivity,

(4) at least one of said metal compounds being a metal chloride,

(5) and at least one of said metal compounds being a compound oftitanium,

(b) Reducing the chloride content of the resulting coprecipitate tobelow about 0.25 percent of the total weight thereof, and

(c) Drying the resulting coprecipitate to produce said coprecipitatedsolid.

PRIOR ART PARTIAL IMPREGNATION METHODS CONTRASTED As indicated, thepresent method, requiring the simultaneous coprecipitation of thehydrogel composite, produces a gelatinous material containing at leastthree different precipitated metal compounds. This must be con trastedwith the method of preparing a three-component solid composite as, forexample, by cogelling only two metal compounds, dehydrating thetwo-component coprecipitate, and thereafter disposing a third metalcomponent onto the coprecipitate by such conventional techniques asimpregnation or sublimation. Although additional metal components can beimpregnated upon the coprecipitate composite produced by dehydration ofthe hydrogel of the present process if desired, it is required that thisinitial coprecipitate be composed of at least three different metalcompounds.

ADVANTAGES OF PROCESS OF PRESENT INVENTION A major reason for thesimultaneous coprecipitation is that it has been found that thecatalysts produced in this manner are very much superior tothree-component catalysts produced by such other methods as by dualimpregnation of a single oxide support, or even those made byimpregnating a third component on a coprecipitated two-componentcarrier. This marked superiority has been exemplified in the comparisonof numerous catalysts. For example, three-component hydrocrackingcatalysts prepared according to the present method have been found topossess higher catalyst activities, lower fouling rates, and betterselectivities than catalysts of similar composition prepared by othermethods. The reasons for this superiority are not completely understoodbut it is be lieved that the reduction of trace contaminants, withperhaps a different and more favorable association of the catalyticfunctions than heretofore obtained, leads to these improved results.

MIXTURE OF THREE DIFFERENT METAL COMPOUNDS IN SOLUTION OR SOL FORM Inaddition to the requirement that at least three different metalcompounds be present in the initial mixture, a number of additionalrestrictions as to the character of these compounds must be met. Thesecompounds must be such that when admixed together, the resulting mixtureis in the form of a solution and/ or a sol, so as to attain uniformdispersion throughout the mixture.

AT LEAST ONE COMPOUND OF A METAL WHOSE SOLID OXIDE HAS CATALYTICISOMERIZA- TION ACTIVITY Further, the present method requires that atleast one of the initial metal salts (that will subsequently beconverted to the corresponding oxide by dehydration of thecoprecipitate) be a compound of a metal whose solid oxide, alone or inadmixture with a different metal compound, possesses catalyticisomerization activity. Such activity is almost universally dependentupon the particular metal oxide being acidic in character. Although anumber of metal oxides, alone or in admixture with a different metalcompound, possess this isomerization activity, a compound of aluminumhas been found to be particularly effective for use in the subjectmethod, because alumina alone and in combination with at least onecompound of at least one different metal has the desired isomerizationactivity. Some metal oxides do not possess the desired isomerizationactivity alone, but can be combined with at least one other metal oxideto produce a mixture having high isomerization activity. For example,silica alone has essentially no isomerization activity, but whencombined with alumina, magnesia, zirconia, titania, thoria, hafnia, orthe like, the mixture has high isomerization activity. Accordingly, inthe present process an aluminum salt should be employed in the initialmixture, or a combination of at least two of the following metal salts:aluminum, magnesium, silicon, titanium, thorium, zirconium, hafnium, andsuch rare earths as cerium, Samarium, and europium. Preferredcombinations are silica-alumina, silica alumina-titania,silica-alumina-zirconia, and silica-magnesia, with silicaalumina-titaniabeing especially preferred.

AT LEAST ONE COMPOUND OF A METAL, THE SULFIDE, OXIDE OR METAL FORM OFWHICH HAS HYDROGENATION ACTIVITY In addition to the use of at least onesalt of a metal Whose solid oxide, alone or in admixture With adifferent metal compound, possesses catalytic isomerization activity, itis required that the initial mixture contain at least one metal compoundprecursor of a Group VI and/ or Group VIII metal, metal sulfide, and/ ormetal oxide hydrogenating component of the final catalytic material.Preferably, at least one salt of the Group VI or Group VIII metals isused in the initial mixture in the present process. At least one salt ofa Group VI metal may be used together with at least one salt of a GroupVIII metal, to produce highly desirable catalysts containing, forexample, as such or in the form of compounds, nickel and molybdenum andnickel and tungsten.

When it is desired to produce by the present method a catalystcomprising nickel or a compound thereof in combination withsilica-alumina, an unusually active catalyst can be made by including atin salt, e. g., stannous chloride, in the initial mixture. It has beenfound that tin or a compound thereof in the final catalyst increases thehydrogenation activity of the nickel or nickel compound,

or at least that the combination has greater hydrogenation activity thannickel or a nickel compound alone.

AT LEAST ONE METAL CHLORIDE The requirement that at least one of themetal components in the initial mixture be a metal chloride presentssomewhat of an anomaly inasmuch as a subsequent step in the preparationinvolves the reduction of the chloride level below about 0.25 percent ofthe total Weight of the final coprecipitate. This anomaly resides in thefact that it has been found that chloride, in addition to certain othercomponents such as sulfates and alkali metal compounds, have adeleterious effect upon the activity, re-' AT LEAST ONE COMPOUND OFTITANIUM When titanium, in the metal, oxide or sulfide form, is presentin the final catalyst prepared by the process of the present invention,as a result of the presence of a compound thereof in the initialmixture, it has been found that catalyst activity is significantlyhigher than when titanium or zirconium in one of these forms is notpresent. The titanium, or compound thereof, preferably is present in thefinal catalyst in the amount of 3 to 15% by weight, based on the totalcatalyst. The higher activity is noted for both denitrification, in thecase of denitrification catalysts, and for hydrocracking, in the case ofhydrocracking catalysts. The higher activity can be obtained by usingzirconium instead of titanium. However, it has been found mostunexpectedly that, While zirconium and titanium are essentiallyequivalent for purposes of activity enhancement of the final catalyst,(a) the catalyst has only moderately good regeneration characteristicswhen it contains zirconium or a compound thereof, but no titanium orcompound thereof, but (b) the catalyst has most excellent regenerationcharacteristics when it contains titanium or a compound thereof.Accordingly, it is necessary for purposes of the present invention thata compound of titanium be present in the initial mixture. A compound ofzirconium also may be present if desired.

When tin, in the metal, oxide or sulfide form, is present in the finalcatalyst prepared by the process of the present invention, as a resultof the presence of a compound of tin in the initial mixture, it has beenfound that, compared with the same catalyst with no tin present: (a) thecracking activity is higher, in the case of a hydrocracking catalyst,(b) the hydrogenation activity is higher, in the case of bothhydrocracking and hydrofining catalysts, and particularly in the case ofa hydrocracking catalyst comprising nickel or a compound thereof andsilica-alumina, and (c) the hydrogenation activity can be controlled inan essentially reversible manner by varying the amount of sulfur presentin the hydrocarbon feed. The tin or compound thereof preferably ispresent in the amount of 1- 30%, preferably 2-15 by weight, based on thetotal catalyst.

The process of the present invention is especially useful for preparingcatalysts containing a molecular sieve component in intimate admixturewith the other catalyst components. The molecular sieve component may beadded, in any desired proportions, preferably 10-45% by weight, morepreferably 15-35% by weight, based on the total finished catalyst.

Especially useful catalysts that can be made by the process of thepresent invention are those having the following combinations ofcomponents, the catalysts being useful in the metallic, oxide or sulfideforms:

(1) Ni (5) Ni W Mo Ti Ti SiOg'AlgOg alone of A1203 with added molecu-(6) Ni lar sieves W (2) Ni Ti Ti A1 0 SiO -Al O alone or (7) Ni withadded molecu- W lar sieves Ti (3) Ni Sn Sn A1203 Ti (8) Ni SiO -Al Oalone or Ti with added molecu- Sn lar sieves SiO -Al O alone or (4) Pdwith added molecu- Ti lar sieves SiO -A1 0 alone or (9) Pd with addedmolecu- Mo lar sieves Ti Any of the catalysts prepared by the presentprocess may be fluorided by conventional methods if desired.

As noted above, it is often preferred that' at least a portion of theinitial mixture be in the form of a sol. For example, it is generallydesirable to employ silica sols when silica is to be a component of thecoprecipitate. In such a case the silica sol can be made by anyconventional procedure. A number of methods for producing such a sol areknown to those skilled in the art. Thus, silica sols can be made byhydrolyzing tetraethyl orthosilicate with an aqueous HCI solution, or inthe presence or absence of solvents, such as alcohols containing 1 to 4carbon atoms per molecule, acetone, methylethyl ketone, and the like.Likewise, silica sols can be prepared by contacting silicontetrachloride with a cold methanol and water solution, or with 95% ethylalcohol, or wit-h cold water or ice. Also, silica sols can be made bycontacting sodium silicate with an ion exchange resin to remove thesodium, or by contact with an acid at a pH of about 2.5 or less.Likewise, if alumina is a desired component of the final coprecipitate,it is entirely feasible to employ alumina sols in the initial mixture. Asol of hydrous alumina can be prepared by reacting aluminum metal withdilute hydrochloric acid or with aluminum chloride solution, with orwithout a catalyst. Also, alumina sols can be prepared by reactingaluminum metal with a weak acid, such as formic or acetic acid.

As discussed above, at least one of the components of the initialmixture must be a metal chloride, and often it is desirable toincorporate at least one sol, such as a silica or alumina sol, in thismixture. Other metal salts can also be present. Suitable salts are thenitrates, citrates, formates, alkoxides and carbonates. Preferably, theacetates are employed. Sulfates are feasible but are often not desirablebecause of the adverse effect that sulfates have on some desirablecatalyst qualities such' as activity and/or fouling rate. If it isdesired that silica be present, the silica component can also be derivedfrom sodium silicate, tetraethyl orthosilicate, silicon tetrachloride,and potassium silicate.

Following formation of the initial mixture,it is then coprecipitated, ata pH between about 5.5 and about 8, by conventional techniques. Thus,the initial mixture, if acidic, can be precipitated by the addition of abase. If the mixture is basic, it can be precipitated with an acid. The

precipitation can be stepwise, as by a form of titration, orsimultaneous, as by mixing of metered solutions in the proper ratios. Itis apparent from the above discussion that any precipitating agentshould preferably not introduce any components in the mixture that aredeleterious, i.e., sulfate or excess alkali, although chloride can beintroduced if necessary since the chloride content of the coprecipitatewill be subsequently reduced by washing and anion exchange.

As an example of a conventional precipitation procedure employed inproducing a silica-alumina-metal containing coprecipitate, sodiumsilicate can be dispersed into a solution of aluminum and metalchlorides containing an excess of acid, such as acetic acid, HCl, HNOetc., to form a silica sol in the presence of dissolved metals. Ammoniacan then be added to the mixture to coprecipitate the component hydrousoxides at a pH of from about 5.5 to 8. Precipitation of an acidicinitial mixture with ammonia, as exemplified, is a preferred techniqueof the present method.

Following precipitation of the hydrous oxides, the excess liquid isremoved, as by filtration. The resulting solid cake, still essentiallycomposed of hydrous oxides, is then treated to remove impurities and toreduce the chloride content to the required level, for example bywashing and ion exchange. Washing can be done in one or more steps,using water or dilute aqueous solutions of ammonium salts of weakorganic acids having a Dissociation Constant K of 10* or less. Saidsalts include ammonium formate, ammonium acetate, ammonium propionateand ammonium butyrate. Ammonium acetate is preferred. Salts of strongerorganic acids are unsatisfactory because the resulting lower pH causesleaching out of valuable metals. Salts of organic acids should be usedbecause organic acids are more decomposable than inorganic acids. Duringor after washing and recovery of the filter cake, the latter ispreferably ion exchanged in the presence of formate ion, acetate ion,propionate ion, butyrate ion, or other similar organic ion derived fromammonium salts of weak organic acids having a Dissociation Constant K of10 or less. The exact function of the formate, acetate or other ionduring the anion exchanging step is unknown, but, when compared tocatalysts prepared by coprecipitation methods where there is no such ionpresent during the exchanging operation, there is no doubt that thepresence of the ion leads to catalysts having superior activities,regenerability and/or fouling rates. With catalysts containing certaincomponents, as for example, nickel, molybdenum and tungsten, thepresence of the ion apparently provides a buffering action at a pH of 6or 7 which minimizes the loss of soluble metals during washing and/oranion exchange of the coprecipitate. Whatever the reason, the presentmethod requires that theanion exchange step be done in the presence ofan ion of the defined class. However, the ion can be introduced into theprocedure at any time up to, and including, the ion exchange step. Thus,the ion can be introduced into the initial mixture. In the case ofacetate ion, for example, the ion can be introduced by acidifying withacetic acid or by employing soluble metal acetates, or in the washingliquid employed to wash the coprecipitate, or, for the first time, byemploying ammonium acetate as the anion exchanger. Preferably, the ionis introduced into the initial mixture and also is present in the washwater in the washing step and also in any subsequent ion exchange step.

The treatment of the anhydrous oxides following precipitation (bearingin mind the requirement discussed above with respect to the presence ofacetate or similar ion) in order to prepare a solid composite suitablefor use as a catalyst, follows practices known in the art insofar as theactual steps of washing, anion exchange and aging is concerned. In anycase, the finally washed, ion exchanged and filtered cake ofcoprecipitate is then dried, as for example, in air or inert gases, to atemperature 7 of from about 150 to 300 F. The coprecipitate is thencalcined, generally at a temperature of from about 750 to 1100 F., inthe presence of an oxygen containing gas. In catalysts wherein thehydrogenating component is at least one metal or compound of molybdenum,tungsten, nickel or cobalt incorporated within a coprecipitatecontaining silica as a component, for example silica in admixture withalumina and titania, it is preferred to thermactivate (heat treat) thecalcined composite by contact with a dried gas at a temperature of fromabout 850 to 1600 F. for a period in excess of about 0.25 hour.

The following examples will further illustrate the process of thepresent invention and various advantages thereof.

EXAMPLES OF PREPARATION OF HYDROFINING CATALYSTS USING TITANIUM COMPOUNDACCORDING TO PROCESS OF PRESENT INVENTION, COMPARED WITH SIMILARPREPARATION METHOD USING A ZIRCONIUM COMPOUND INSTEAD OF A TITANIUMCOMPOUND, AND CHARACTERISTICS AND USE OF FRESH AND REGENERATED CATA-LYSTS SO PREPARED Catalyst 1 (Comparison Catalyst) Solution IA Parts byWt. oi Solution IIA Parts by Wt. of Components Solution IA ComponentsSolution IB A. Preparation:

(a) Acidic Solutions 33. 1 NiClz 33. 1 79. 8 A1013 79. 8

8. 1 ZlOClz... (None) (None) 'liClr 13.3 25.1 (N320) (3.3 SiO2) 25. 1 53Acetic Acid 53 2, 074 H2O 2, 069

Solution IB Parts by Wt. oi Solution IIB Parts by Wt. of ComponentsSolution IIA Components Solution IIB (b) Alkaline Solutions W a 25.3 W0325.3 (None) NaOH. 7. 5 108 NHqOH. 108 H2O 823 H2O 815.5 (0) Mixture ofAcidic and Akaline Solutions Solutions IA and HA, acidic solutions ofmetals and sodium silicate, were neutralized with alkaline tungstenSolutions 113 and HE, respectively, by mixing Solution IA with SolutionIB, and by mixing Solution IIA with Solution 1113. Each mixture was agel slurry with a pH of about 7.0. In each case the gel was filtered,dried to about 70% volatiles, formed into dia. particles, washed and ionexchanged with 1% ammonium acetate solution to reduce the sodium andchloride contents to a low level, including less than 0.25 wt. percentchloride, dried and calcined at 950 F.

Catalyst 1 Catalyst 2 Component Wt. Percent of Component Wt. Percent ofTotal Catalyst Total Catalyst B. Composition of Final Fresh Catalyst,Prior to NiO 19. 1 19.1 Sulfiding. 25. 3 25. 3 5. 6 5. 6 30. 5 30. 5SiOz 19. 5 19. 5

Catalyst 1 Catalyst 2 C. Area and Pore Volume of Final Fresh Catalyst,

Prior to Sulfiding:

Area, Mfi/gram 299 360 Pore Volume, CC./gram 0.39 0.353

Fresh Catalysts 1 and 2 each were sulfided with dimethyl disulfide in aconventional manner.

d1 g E. Use of Fresh Sulfided Catalysts 1 and 2 for Hydro- FreshCatalysts 1 and 2 were used in separate runs to hydrofine a Midway gasoil with a boiling fining.

range of 500900 F., containing 3,000 p.p.m. organic nitrogen. Each runwas conducted at Run With Catalyst 1 Run With Catalyst 2 F. CatalystFouling Rate, F. Per Hour, During 0. 026 0. 035

Runs of E. G. Regeneration Catalysts 1 and 2, after being used untilregeneration was required, each were regenerated with anoxygen-containing gas in a conventional manner.

Catalyst 1 Catalyst 2 H. Area and Pore Volume oi Rogonoratud Catalyst,

Prior to Sulfidlng:

Area, Mfilgramw 204 227 Pore Volume, cc./g 0. 351 0. 325

I. Sulfiding J. Use of Regeneratod Sulfided Catalysts l and 2 forHydrolining.

temperature, wit

Rcgenerated Catalysts 1 and 2 were resulfided with dimethyl disulfide ina conventional manner.

Regcnerated and resulfidecl Catalysts 1 and 2 were used in separate runsto hydrofine the Midway gas oil described under E, under the conditionsdescribed under E, except for starting h the organic nitrogen content ofthe liquid product again being maintained at 0.3 p.p.m. by adjustment ofcatalyst temperature, which was required to be 758-761 F. at the startof the runs.

Run With Regenerated Catalyst 1 Run With Regenerated Catalyst 2 K.Catalyst Fouling Rate, F. Per Hour, During Runs of J.

EXAMPLES OF PREPARATION CATALYST USING PROCESS OF PRESENT INVENTION, ANDCHARACTERISTICS AND USE OF FRESH AND REGENERATED CATALYSTS SO PREPAREDOF HYDROCRACKING Solution Parts By Wt. Of Components olution A.Preparation:

(a) Acidic Solution NiCh Component Parts By Wt. Of

Total Catalyst B. Composition Of Final Fresh NiO 12. 7 Catalyst Prior ToSulfiding. 6

C. Area And Pore Volume of Final Fresh Catalyst 3 Prior To Sulfiding:

Area, Mfi/grarn Pore Volume, ee./gram 0. 369 D. Sulfiding Catalyst 3 wassulfided With dimethyl dis fide in a conventional manner. E. Use OfFresh Sulfided Cata- Fresh Catalyst 3 was used to hydrolyst 3 ForHydrocracking. crack, without prior hydrofimng, an Arabian gas oil witha boiling range 6501,000 F., containing 600 p.p.m. organic nitrogen. Thehyfrocracking conditions were 1.5 LHSV, 1,200 p.s.i.g. hydrogen exit gasrate of 6,000 s.c.f. per barrel of gas oil feed, on a once through oiland hydrogen basis, at a constant conversion of 50% per pass to productsboiling below 050 F., the conversion being obtained at the start with acatalyst temperature of 741 F., and being maintained by subsequentadjustment of catalyst temperature.

F. Catalyst Fouling Rate,

F. Per Hour, Of Fresh Catalyst 3 During Run 0i E. 0.032 G. RegenerationCatalyst 3, after being used until regeneration was required, wasregenerated with an oxygeiicontaiiiing gas in a conventional manner.

H. Area And Pore VolumaOf Regenerated Catalyst Prior To Sulfidin Area,M1 gram 282 Pore Volume, cc./gram 0. 332

I. Sulfiding i. Regenerated Catalyst 3 was resulfided with dlmethyldlsulnde in a conventional manner.

Regenerated and resulfided Catalyst 3 was used to hydrocrack, withoutprior hydrofining, the Arabian gas oil described under E, under theconditions described under E, except for starting temperature, with theconversion again being maintained at 50% per pass to products boilingbelow 650 F., the conversion being obtained at the start with a catalysttemperature of 743 F., and being maintained by subsequent adjustment ofcatalyst temperature.

J. Use Of Regenerated Sulfided Catalyst 3 For Hydrocracking.

K. Catalyst Fouling Rate,

F. Per Hour, Of Regenerated Catalyst 3 During Run Oil.

From the foregoing it may be seen. that regenerated Catalyst 3 had alower fouling rate than when it was fresh, and was able to accomplishthe same per-pass conversion of the feed at a starting temperature on ly2 F.

higher than when it was fresh. Catalyst 3 regeneratedv better thanCatalyst 2, in that upon regeneration the fouling rate of Catalyst 2 washigher than when Catalyst 2 was fresh, because of the higher titaniacontent of Catalyst 3. In any case, the titania apparently serves a dualpurpose-it hinders the growth of metal crystallites while the catalystis in service, and acts during regeneration as an oxidation catalyst topromote combustion of carbonaceous deposits.

As has been described and exemplified above, the present catalystpreparation method is particularly suitable for producing hydrofining,i.e., hydrodenitrification and hydrodesulfurization, catalysts and forproducing hydrocracking catalysts. The specific conditions forconducting these various reactions are well known in the art. However,these reactions have many features in common and are herein genericallytermed hydroprocessing reactions. These reactions all are directed tothe conversion of hydrocarbonaceous material and are conducted in thepresence of added hydrogen since these reactions will all consume atleast 250 s.c.f. of hydrogen per barrel of feed contacted. The reactiontemperatures will be in the range of from about 500 to 1000 F.,preferably from about 500 to 900 F., and reaction pressures will be inthe range of from about 200 to over 3000 p.s.i.g., and preferably, inthe range of from about 300 to 2500 p.s.i.g., depending upon theparticular feed employed. Feed rates will generally be in the range offrom about 0.1 to 10.0 LHSV. Accordingly, catalysts prepared by thesubject method are especially suited for use in such hydroprocessingreactions.

Although a number of catalysts made according to the present inventionhave been exemplified, it is apparent that variations could be made inthe present method without departing from the spirit of the invention,and all such variations that fall within the scope of the appendedclaims are intended to be embraced thereby.

What is claimed is:

1. A method for producing a coprecipitated solid containing at least onemetal oxide and having a minimum of three components therein, saidcomponents having been coprecipitated simultaneously, which comprisesthe steps:

(a) Coprecipitating a mixture of at least three different metalcompounds at a pH of from about 5.5 to about 8, said mixture having allof the following characteristics,

(1) said mixture being a solution or a sol,

(2) at least one of said metal compounds being a compound of a metalwhose solid oxide has catalytic isomerization activity, alone or inadmixture with a different metal compound,

(3) at least one of said metal compounds being a compound of a metal,the sulfide, oxide or metal form of which has catalytic hydrogenationactivity,

(4) at least one of said metal compounds being a metal chloride,

(5) and at least one of said metal compounds being a compound oftitanium,

(b) Reducing the chloride content of the resulting coprecipitate tobelow about 0.25 percent of the total weight thereof, and

(c) Drying the resulting coprecipitate to produce said coprecipitatedsolid.

2. The method as in claim 1 wherein said mixture of at least threedifferent metal compounds contains a molecular sieve component.

3. The method as in claim 2 wherein said mixture of at least threedilferent metal compounds contains a compound of nickel.

11 12 4. The method as in claim 3 wherein said mixture of 3,222,27312/1965 Flinn et a1. 208-112 at least three different metal compoundscontains a com- 3,236,762 2/ 1966 Rabo et a1. 208-111 pound of tungsten.3,250,728 5/1966 Miale et a1. 252-439 References Cited 3,280,040 11/1966Jalfe 252-439 UNITED STATES PATENTS 3,008,895 11/1961 Hansford et a1.208-112 DANIEL WYMAN Pmary Examme" 3,159,569 12/1964 Hansford 208-110 P.E. KONOPKA, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,401,125 September 10, 1968 Joseph Jaffe It is certified that errorappears in the above identified patent and that said Letters Patent arehereb3 corrected as shown below:

Columns 7 and 8, in the table, the sub-heading of the second column,opposite "(b) Alkaline Solutions", "Parts by Wt. of Solution IIA" shouldread Parts by Wt. of Solution IB same table, the sub-heading of thefourth column, opposite "(a) Acidic Solutions", "Parts by Wt. ofSolution IB" should read Parts by Wt. of Solution IIA Column 9, lines 6to 8, cancel "A hydrocracking catalyst, Catalyst 3, was prepared inexactly the same manner as Catalysts l and 2, except that the twostarting solutions were as follows:" and insert the same after "A.Preparation:" in line 1, first column of the table in column 9.

Signed and sealed this 10th day of February 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR.

Attesting Officer Commissioner of Patents

